Method for preparing sulfated metal oxide catalyst for chlorination, and chlorination method using sulfated metal oxide catalyst

Patent metadata

Field	Value
Publication number	US-2021069689-A1
Application number	US-201816643410-A
Country	US
Kind code	A1
Filing date	Aug 30, 2018
Priority date	Aug 31, 2017
Publication date	Mar 11, 2021
Grant date	—

Abstract

The present invention relates to a method for preparing a sulfated metal oxide catalyst for chlorination, and a method for producing a reaction product containing methyl chloride (CH3Cl) by using the sulfated metal oxide catalyst. A sulfated zirconia catalyst and a sulfated tin oxide catalyst are disclosed as the sulfated metal oxide catalyst for chlorination.

First claim

1 . A method for preparing a sulfated zirconia catalyst for chlorination, the method comprising:
a step a) of forming a mixed solution by mixing an amine reactant and a zirconium precursor containing an oxygen element and dissolving the mixture in a solvent; a step b) of forming a gel-type product by heating and stirring the mixed solution formed in the step a); a step c) of forming zirconia (ZrO 2 ) by calcining the gel-type product formed in the step b); and a step d) of preparing sulfated zirconia (SO 4 2− /ZrO 2 ) by impregnating the zirconia formed in the step c) with a solution containing a sulfated agent and evaporating the solvent by performing heating.

2 . The method of claim 1 , wherein the amine reactant is selected from aspartic acid, glutamic acid, glycine, taurine, sarcosine, iminodiacetate, alanine, phenylalanine, isoleucine, histidine, lysine, arginine, and water-soluble salts thereof, and
the zirconium precursor containing an oxygen element is selected from zirconyl chloride octahydrate (ZrOCl 2 .8H 2 O) and zirconium(IV) oxynitrate hydrate (ZrO(NO 3 ) 2 .xH 2 O).

3 . The method of claim 1 , wherein, in the step a), the amine reactant and the zirconium precursor containing an oxygen element are mixed at a molar ratio of 1:0.5 to 1:5.

4 . (canceled)

5 . (canceled)

6 . (canceled)

7 . (canceled)

8 . The method of claim 1 , further comprising a step e) of calcining the sulfated zirconia prepared in the step d) at 500 to 800° C. under an air atmosphere.

9 . (canceled)

10 . (canceled)

11 . (canceled)

12 . A sulfated zirconia catalyst for chlorination.

13 . The sulfated zirconia catalyst for chlorination of claim 12 , wherein a content of sulfate ions (SO 4 2− ) in the catalyst is 10.0 wt % or more.

14 . The sulfated zirconia catalyst for chlorination of claim 12 , wherein a total acid density of the catalyst measured by ammonia temperature-programmed desorption (NH 3 -TPD) is 8 mmolNH 3 /g or more, and
a proportion of an acid density of a very strong acid site (an acid site at which an acid site desorption temperature is higher than 400° C.) is 80% or more of the total acid density.

15 . (canceled)

16 . A method for producing a reaction product containing methyl chloride (CH 3 Cl) by performing a chlorination reaction on a reactant containing methane (CH 4 ) under a presence of the sulfated zirconia catalyst for chlorination prepared by the preparation method of claim 1 .

17 . The method of claim 16 , wherein the chlorination reaction is performed:
(i) at a temperature of 200 to 550° C.; (ii) at a molar ratio of the reactant containing methane to chlorine (Cl 2 ) gas of 1/1 to 10/1; and (iii) at a gas hourly space velocity (GHSV) of each of the reactants of 100 to 3000 cc/g/h.

18 . A method for preparing a sulfated tin oxide (SO 4 2− /SnO 2 ) catalyst for chlorination, the method comprising:
a step a) of dissolving a tin precursor in a solvent and inducing hydrolysis of the tin precursor by adding aqueous ammonia until a pH of a solution reaches 7.5 or more; a step b) of obtaining a solid product by filtering a precipitate obtained by the hydrolysis in the step a); a step c) of producing tin hydroxide (Sn(OH) 4 ) by drying the solid product obtained in the step b); a step d) of obtaining a solid product by impregnating the tin hydroxide (Sn(OH) 4 ) produced in the step c) with a solution containing a sulfated agent, stirring the solution and performing filtering; a step e) of drying the solid product obtained in the step d); and a step f) of producing sulfated tin oxide by calcining the solid product dried in the step e).

19 . The method of claim 18 , wherein the tin precursor is at least one selected from SnCl 2 , SnCl 2 .2H 2 O, CH 3 (CH 2 ) 3 SnCl 3 , SnCl 4 .5H 2 O, and SnCl 4 .

20 . (canceled)

21 . (canceled)

22 . (canceled)

23 . (canceled)

24 . A sulfated tin oxide catalyst for chlorination.

25 . The sulfated tin oxide catalyst for chlorination of claim 24 , wherein a content of sulfate ions (SO 4 2− ) in the catalyst is 5.0 wt % or more.

26 . The sulfated tin oxide catalyst for chlorination of claim 24 , wherein a total acid density of the catalyst measured by ammonia temperature-programmed desorption (NH 3 -TPD) is 3.0 mmolNH 3 /g or more, and
a proportion of an acid density of a very strong acid site (an acid site at which an acid site desorption temperature is higher than 400° C.) is 50% or more of the total acid density.

27 . The sulfated tin oxide catalyst for chlorination of claim 24 , wherein a BET specific surface area of the catalyst is 80 to 200 m 2 /g.

28 . (canceled)

29 . A method for producing a reaction product containing methyl chloride (CH 3 Cl) by performing a chlorination reaction on a reactant containing methane (CH 4 ) under a presence of the sulfated tin oxide catalyst for chlorination prepared by the preparation method of claim 18 .

30 . The method of claim 29 , wherein the chlorination reaction is performed:
(i) at a temperature of 200 to 550° C.; (ii) at a molar ratio of the reactant containing methane to chlorine (Cl 2 ) gas of 1/1 to 10/1; and (iii) at a gas hourly space velocity (GHSV) of each of the reactants of 100 to 3000 cc/g/h.

31 . A method for producing a reaction product containing methyl chloride (CH 3 Cl) by performing a chlorination reaction on a reactant containing methane (CH 4 ) under a presence of the sulfated zirconia catalyst for chlorination of claim 12 .

32 . A method for producing a reaction product containing methyl chloride (CH 3 Cl) by performing a chlorination reaction on a reactant containing methane (CH 4 ) under a presence of the sulfated tin oxide catalyst for chlorination of claim 24 .

Assignees

• Korea Res Inst Chemical Tech

Inventors

• Chae Ho Jeong
• Kim Young Min
• Kim Jip
• Kim Hyung Ju

Classifications

• B01J23/14

  of germanium, tin or lead · CPC title

• B01J37/082

  Decomposition and pyrolysis · CPC title

• B01J37/033 Primary

  Using Hydrolysis · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title